Prcis: 240-degree and 360-degree goniotomy (GT) demonstrated similar efficacy in intraocular pressure (IOP) reduction, both outperforming 120-degree GT in patients with juvenile open angle glaucoma (JOAG) at postoperative 6-month follow-up.
Objective: To compare the surgical efficacy and safety of 120-degree, 240-degree, and 360-degree GT for patients with JOAG.
Patients And Methods: This multicenter retrospective study included 102 eyes of 102 patients with JOAG, who underwent GT with a follow-up of at least 6 months.
Here we report a highly diastereoselective cyano group transfer radical cyclization reaction to construct 5/6-fused bicyclic ring systems that bear three contiguous and congested stereogenic elements, with 100% atom economy under catalyst-free and near-ultraviolet light irradiation conditions. Mechanistic investigations and density functional theory calculations suggest that the diastereoselectivity is governed by the conformational distribution of the triplet diradical intermediate and the rate of reverse intersystem crossing (RISC) before radical coupling.
View Article and Find Full Text PDFBMC Palliat Care
October 2024
Regiochemical control is a central subject in the field of synthetic chemistry. Here we unveil an innovative approach for the branch-selective allylic C-H amination of α-alkenes with amine nucleophiles facilitated by phosphoramidite-palladium catalysis. A diverse array of α-alkenes has been effectively utilized to produce a variety of structurally distinct allylamines with moderate to excellent regioselectivity.
View Article and Find Full Text PDFNat Commun
July 2024
Cu catalyses electrochemical CO reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six phenyl-1H-1,2,3-triazole derivatives to form stable coordination polymer catalysts with homogenized, single-site Cu active sites. Electronic structure modelling, X-ray absorption spectroscopy, and ultraviolet-visible spectroscopy show a widely tuneable Cu electronics by modulating the highest occupied molecular orbital energy of ligands.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2023
Enantioconvergent catalysis enables the conversion of racemic molecules into a single enantiomer in perfect yield and is considered an ideal approach for asymmetric synthesis. Despite remarkable advances in this field, enantioconvergent transformations of inert tertiary C-H bonds remain largely unexplored due to the high bond dissociation energy and the surrounding steric repulsion that pose unparalleled constraints on bond cleavage and formation. Here, we report an enantioconvergent Pd-catalyzed alkylation of racemic tertiary allylic C-H bonds of α-alkenes, providing a unique approach to access a broad range of enantioenriched γ,δ-unsaturated carbonyl compounds featuring quaternary carbon stereocenters.
View Article and Find Full Text PDFThe diverse functionalization of 1,3-butadiene provides wide applicability toward the synthesis of abundant and useful allylic compounds. Here, we describe a three-component and redox-neutral assembly of readily available C═X compounds, 1,3-butadiene, and various nucleophiles by merging photoredox and nickel catalysis, enabling the rapid synthesis of structurally diverse homoallyl amines and homoallylic alcohols.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2023
J Am Chem Soc
December 2021
Asymmetric functionalization of the C(sp)-H bond is an attractive yet challenging strategy to achieve versatile bond-forming events, enabling the precise assembly of molecular complexity with minimal manipulation of functional groups. Here, we report an asymmetric C(sp)-H/C(sp)-H umpolung coupling of -allylimine and coordinating α-aryl carbonyls by using chiral phosphoramidite-palladium catalysis. A wide variety of α-heteroaryl ketones and 2-acylimidazoles are nicely tolerated to open a convenient and tunable avenue for efficient synthesis of enantioenriched β-amino-γ,δ-unsaturated carbonyl derivatives with high levels of regio- and stereoselectivities, capable of providing a key intermediate for asymmetric synthesis of Focalin.
View Article and Find Full Text PDFThis research aims to investigate the salience of mothers' emotional expressivity and its links with adolescents' emotional wellbeing and expressivity in an urban society endorsing more individualism and a rural society ascribing to more collectivism. By comparing Chinese urban ( = 283, = 14.13) and rural ( = 247, = 14.
View Article and Find Full Text PDFChem Commun (Camb)
July 2021
Asymmetric allylic C-H alkylation of 1,4-pentadienes with α-angelica lactones has been developed by tri-axial phosphoramidite-palladium catalysis. This reaction can tolerate a range of functional groups under mild conditions, furnishing versatile chiral γ,γ-disubstituted butenolides in high yields with good to high levels of stereoselectivity.
View Article and Find Full Text PDFAsymmetric functionalization of inert C(sp)-H bonds is a straightforward approach to realize versatile bond-forming events, allowing the precise assembly of molecular complexity with minimal functional manipulations. Here, we describe an asymmetric photocatalytic C(sp)-H bond addition to α-substituted acrylates by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst and chiral phosphoric acid as a chiral proton-transfer shuttle. This protocol is supposed to occur via a radical/ionic relay process, including a TBADT-mediated HAT to cleave the inert C(sp)-H bond, a 1,4-radical addition, a back hydrogen abstraction, and an enantioselective protonation.
View Article and Find Full Text PDFObjectives: This study aims to assess the cost-effectiveness of three renal replacement therapy (RRT) modalities as well as proposed changes of scheduled policies in RRT composition in Guangzhou city.
Methods: From a payer perspective, we designed Markov model-based cost-effectiveness analyses to compare the cost-effectiveness of three RRT modalities and four different scheduled policies to RRT modalities in Guangzhou over three time horizons (5, 10 and 15 years). The current situation (scenario 1: haemodialysis (HD), 73%; peritoneal dialysis (PD), 14%; kidney transplantation (TX), 13%) was compared with three different scenarios: an increased proportion of incident RRT patients on PD (scenario 2: HD, 47%; PD, 40%; TX, 13%); on TX (scenario 3: HD, 52%; PD, 14%; TX, 34%); on both PD and TX (Scenario 4: HD, 26%; PD, 40%; TX, 34%).
Background: Job evaluation has been widely used to establish a foundation for internal equity and other human resource functions. The United Kingdom adopts the National Health Service (NHS) Job Evaluation scheme to determine the pay bands for most NHS staff and ensure equal pay for work of equal value. The challenges of recruiting and retaining physicians in Chinese public hospitals have heightened the need for a reliable job evaluation system to ensure the equality of physician compensation.
View Article and Find Full Text PDFAppl Health Econ Health Policy
March 2021
Background: Kidney replacement therapy (KRT) is a lifesaving but costly treatment for patients with end-stage kidney disease (ESKD). The objective of this study was to review full economic evaluations comparing KRT modalities specified as hemodialysis (HD), peritoneal dialysis (PD), and kidney transplantation (KT) for patients with ESKD.
Methods: We conducted a systematic review of the literature from PubMed, Embase, EconLit (EBSCO), Web of Science, Cochrane Library, National Health Service Economic Evaluation Database (NHS EED), Centre for Reviews and Dissemination (CRD) Database of Abstracts of Reviews of Effects (DARE), and CRD Health Technology Assessment Database from inception until 5 January 2020.
Asymmetric functionalization of inert C-H bonds is undoubtedly a synthetically significant yet challenging bond-forming process, allowing for the preparation of densely functionalized molecules from abundantly available feedstocks. In the past decade, our group and others have found that trivalent phosphorus ligands are capable of facilitating Pd-catalyzed allylic C-H functionalization of α-alkenes upon using -quinone as an oxidant. In these reactions, a 16-electron Pd(0) complex bearing a monodentate phosphorus ligand, a -quinone, and an α-alkene has been identified as a key intermediate.
View Article and Find Full Text PDFTop Curr Chem (Cham)
December 2019
Asymmetric metal/organo relay catalysis, utilizing a metal complex and a chiral organocatalyst in a one-pot cascade reaction, is aimed to sequentially impart activation on multiple steps by distinct catalysts. Such a catalysis merges the advantages of both metal catalysis and organocatalysis, providing step-economy, and, more importantly, the potential to achieve inaccessible reactivity by a single catalyst. Chiral phosphoric acids are among the most robust organocatalysts, rendering a broad range of enantioselective bond-forming reactions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2019
Branched selectivity in asymmetric allylic C-H alkylation is enabled by using 2-acylimidazoles as nucleophiles in the presence of a chiral phosphoramidite-palladium catalyst. A wide range of terminal alkenes, including 1,4-dienes and allylarenes, are nicely tolerated and provide chiral 2-acylimidazoles in moderate to high yields and with high levels of regio-, and enantio-, and E/Z-selectivities. Mechanistic studies using density-functional theory calculations suggest a nucleophile-coordination-enabled inner-sphere attack mode for the enantioselective carbon-carbon bond-forming event.
View Article and Find Full Text PDFMonodentate phosphorus ligands have been found to enable the palladium-catalyzed allylic C-H alkylation reaction of terminal alkenes with a wide variety of carbon nucleophiles. Moreover, an asymmetric allylic C-H alkylation of terminal alkenes with pyrazol-5-ones has been established in the presence of chiral phosphoramidite ligand and chiral phosphoric acid as co-catalyst. Mechanistic studies suggest that a ternary Pd(0) complex, coordinated with a monodentate phosphorus ligand, benzoquinone, and alkene, is most likely to be an active species.
View Article and Find Full Text PDFAn asymmetric allylic C-H alkylation of allyl ethers has been established by chiral phosphoramidite-palladium catalysis, affording a wide variety of functionalized chiral 2-acylimidazoles in moderate to high yields and with high levels of enantioselectivity. Moreover, this protocol could be applied to a concise asymmetric synthesis of a tachykinin receptor antagonist.
View Article and Find Full Text PDFIn the presence of visible-light photoredox and chiral phosphate catalysts, a novel asymmetric Friedel-Crafts reaction of indoles and readily accessible α-amino acid derived redox-active esters is established to afford enantioenriched 1-indolyl-1-alkylamine derivatives in moderate to high yields and with high levels of enantioselectivities. This method not only shows a mild and efficient alternative for the in situ generation of N-acyl imines but also indicates the feasibility of a multicatalyst system for asymmetric photoredox catalysis.
View Article and Find Full Text PDFThe asymmetric allylic alkylation (AAA), which features employing active allylic substrates, has historical significance in organic synthesis. The allylic C-H alkylation is principally more atom- and step-economic than the classical allylic functionalizations and thus can be considered a transformative variant. However, asymmetric allylic C-H alkylation reactions are still scarce and yet underdeveloped.
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